Algicidal and sanitizing compositions



United States Patent O "ice ALGICIDAL AND SANHTZENG CQMPSlH/NS Harold E. Antonides and Ralph L. Dietchweiler, Kankakee, ill., assignors to Armour Pharmaceutical @oml pany, Chicago, lil., a corporation of Delaware No Drawing. Filed Jan. i9, i962, Ser. No. 167,4@ 9 Claims. (Cl. 167-22) This invention relates to algicidal and sanitizing compositions and method of preparing the same, and more particularly to compositions for controlling various types of organisms found in water systems.

In swimming pools, water cooling systems and other systems in which water is employed, clogging and troublesome situations are produced through the action of algae and slime and acid-producing organisms. Chlorine and bromine are commonly used to inhibit or destroy microorganisms, but they have many deciencies. In swimming pools, they are irritating to skin and eyes of swimmers, and they are relatively ineffective against certain commonly-occurring organisms.

We have discovered that chlorine may be employed in reduced `amounts and without the skin or eye irritating effects, and in synergistic action with certain quaternary ammonium salt and amine compounds, while at the same time producing much more effective action against algae, fungi, bacteria, etc., and for maintaining the water systems clear and free of such organisms.

A primary object, therefore, of the invention is to provide a synergistic combination of nitrogenous compounds with chlorine which is effective at low concentrations in aqueous fluid-s for controlling algae, bacteria, and fungi. A further object is to provide a non-irritating and non-toxic germicidal composition edective in combating the conditions described above. Other specic objects and advantages will appear as the specification proceeds.

In one embodiment of our invention, we combine chlorine with a nitrogenous composition consisting preferably of three components, namely, an alkyl primary .famine salt having from 10 to 18 carbon atoms, a quaternary ammonium salt having at least one alkyl group consisting of from 10 to 18 carbon atoms, and a quaternary ammonium salt having at least one alkyl group consisting of from l to 18 carbon atoms and containing from 2 to about 25 moles of an alkylene oxide substituent of from 2 to 4 carbon atoms. At the concentrations employed for eiective algicidal and sanitizing use, the nitrogenous and chlorine-nitrogenous compositions are found to be virtually non-irritating, non-toxic, odorless, colorless, low-foaming, resistant -to inactivation by cornmon impurities, such as water hardness, and are highly stable and long-acting non-volatile preparations.

The rst component of the nitrogenous combination is an alkyl primary amine salt having from about to 18 carbons in the alkyl chain. Various salts such as the hydrochloride, acetate, nitrite, sulfate, hydrobromide7 and hydroiodide may be used, although we ordinarily prefer to use the hydrochloride salt. Cptimally we supply dodecylamine hydrochloride to our combinations; hov ever, for certain selected purposes, such as high corrosion inhibition, other salts including the nitrite may be preferred.

As the second component of the nitrogenous germicidal combinations, we supply a quaternary ammonium salt having at least one alkyl group, the alkyl group having from about 10 to 18 carbons. For general usage, the anion portion of this salt may be the chloride, but again in certain cases, for example fuel storage, nitrite salts are preferred because of their higher corrosion inhibition eiect. Also for general use, we prefer that the alkyl groups be of longer chain length than is ordinarily supplied for Quaternary ammonium compounds selected for their germicidal activity. Benzylquats, soya compounds, and methyl sulfate salts are examples of other quatertilll Patented Aug, 17, 1965-,

nary ammonium compounds which are suitable as the second component of the nitrogenous combinations.

As the third component of the nitrogenous combinations, one may employ `a quaternary ammonium salt having at least one alkyl group of from 10 to 18 carbons which additionally contains from about 2 to 25 moles of an alkylene 4oxide having '.2 to 4 carbons. We prefer that these compounds contain 2 to 10 moles of propylene oxide or ethylene oxide. Various anions such as the chlorides may be utilized in this component, but methyl sulfate is usually preferred unless high corrosion resistance is important, in which case the quaternary ammonium nitrite may be substituted for the methyl sulfate anion.

With the above-mentioned nitrogenous compositions having the three described components, we combine chlorine, using preferably an organic water-soluble chlorinereleasing agent such as sodium or potassium dichloro triazinetrione or trichloro triazinetrione. Dichloro triazinetrione or trichloro triazinetrione may also be employed with an alkaline agent, such as sodium bicarbonate or carbonate, etc. The hypochlorites of alkaline metals may be employed as chlorine sources. Calcium hypochlorite particularly is useful.

The three components of the nitrogenous compositions are preferably employed in about equal proportions, but yit is realized that the microorganism inhibitory etiects can be obtained where such components are varied through a wide range of concentrations. For example, in a cornposition in which 5 parts of the alkylene oxide quaternary compound are employed, this compound may be blended with about 1 to 10 parts of the alkyl ammonium salt and with about l to 10 parts of the quaternary ammonium salt. As stated above, for general use, a suiable preparation is prepared by blending equal parts by weight of the three components.

The method of blending the combination of nitrogenous components is in no way critical, but we nd this may be easily accomplished by preparing the alkylarnine salt in an isopropanol or isopropanol-vater solution and `adding the other two components, preferably in isopropanol, to attain a nal concentration in the stock preparation no higher than 72% (w./v.) of total active ingredients. This limit is imposed merely because of physical considerations, as the combinations become undesirably viscous at concentrations above 72% active ingredients.

The dried nitrogenous composition may then be cornbined with an essentially anhydrous organic or inorganic chlorine-releasing component. The proportions of chlorine may also be varied through a relatively wide range to bring about the synergistic etect in which germicidal effectiveness is greater than the added eiects of the chlorine and the nitrogenous composition when employed separately, while at the same time eliminating the irritating and toxic etiects that normally tiow `from the use of chlorine. For example, at use dilutions in combination with the nitrogenous composition in which the three components are each employed in the amount of 0.375 ppm. (parts .per million), we prefer to employ at least 0.l ppm., and preferably 0.5 to l ppm., of chlorine. Again, when the nitrogenous composition is employed in the proportion of 2.25 ppm., we prefer to use at least 0.1 and preferably 0.25 `to 1 ppm., of chlorine. lf desired, the chlorine -may be used up to 10 ppm., but it is found that there is little advantage in going above l ppm. when the chlorine is used with the nitrogenous composition in the proportions stated (0.375 to 0.75 p.p.rn. for each component or 1.125 Ito 2.25 ppm. of the nitrogenous composition).

By way of specific example, when it is desired to clear .s a swimming pool which is heavily overgrown with algae or is green by reason or" the algae present, We prefer to employ the chlorine-nitrogenous composition in which each of the nitrogenous components is present in the amount of about .75 p.p.m. and with the chlorine present in the amount of about 1 ppm. After the Water has been cleared, it may be maintained in clear and satisfactory condition by the same `amount of nitrogenous compound (with components totalling 2.25 ppm.) with a content of .25 ppm. of chlorine; in fact, With .25 ppm. of chlorine, the total amount of the nitrogenous compounds may be reduced to 1.25 ppm. From the foregoing, it will be seen that the range of chlorine employed with the nitrogenous compositions may vary from .1 to 19 ppm., but preferably is between .25 ppm. to 1 ppm. At the `same time, the nitrogenous composition may vary from .1 to 5 ppm., the preferable range being between .125 ppm. and 2.125 ppm.

The treatment of Water containing the microorganisms to be inhibited or destroyed may be carried on by using the nitrogenous compounds and chlorine in liquid form, lor the components may all be incorporated in a single dry composition. The combination of the ingredients in dry form has the advantage of enabling the composition to be packaged in unit dosage quantities and in a highly stable condition.

The following examples are given only to aid in understanding the invention, and it is to be understood that the invention is not lrestricted to the particular materials, proportions, or procedures set forth.

EXAMPLE I The nitrogenous composition (herein abbreviated N.C.) consisting of equal proportions of the components as described hereinbefore was employed at 4.5 ppm., 2.25 ppm. and 1.125 ppm. active ingredients, `and With chlorine at 1.0 ppm., 0.5 ppm. and 0.25 ppm., individually and in `combination as set out in the following Table 1 and in which the N.C. liquid product is employed, the chlorine being provided by sodium hypochlorite solution:

Combination of the low levels of the nitrogenous composition (NC.) With chlorine demonstrated greater activity against the Chlorella type algae than either matcrial individually at higher concentrations. The combination or" 2.25 ppm. active ingredients of N.C. with 1.0 ppm. chlorine had an activity against Chlorella greater `than the same concentrations individually. The same observation also applies to the combination of 2.25 ppm. active ingredients of N.C. with 9.5 ppm. chlorine to an even greater degree. Combinations of 2.25 ppm. and 1.125 ppm. N.C. with 0.25 p.p.m. chlorine were comparable or perhaps superior to 0.5 ppm. chlorine alone. A level of 0.5 ppm. chlorine is a standard treatment level tor swimming pool water to maintain it in compliance with accepted practice and health regulations.

EXAMPLE Il ln the following example, the nitrogenous compound (N.C.) was combined With chlorine-releasing chemicals to form a dry product, the formulation being as follows:

Percent Dodecylamine hydrochloride 6.34 rfrimethyl alkyl ammonium chloride 6.34

Methyl alkyl dipolyoztypropyiene ammonium methyl sulfate 6.34 Potassium dichloro(s) triazinetrione 27.73 Sodium biphosphate 51.20 Silica 0.05

In initial attempts to form a dry composition, considerable diiiculty was e: perienced because of the gummy or paste-like character of the quaternary compounds when the isopropanol was removed. Applicants discovered that by combining with the nitrogenous composition large amount of sodium biphosphate or other Water-soluble extender, it was possible to spray dry the material. The dried material was then mixed With dry potassium dichloro triazinetrione and with silica to form the finished product.

The foregoing composition was then used in the treatment of sewage organisms, and the results are set out in the `following table:

Table L Algcidal activity of N.C. and chlorine against Chlorella pyrenoidosa N.C., p.p.rn Untrcated 4.5 4. 5 4. 5 2. 25 2. 25 2. 25 1.125 1.125 1.125 4. 5 2. 25 1.125 0 0 0 Chlorine, ppm. Control 1.0 0. 5 0.25 1. 0 0. 5 0.25 1. 0 0. 5 0.25 0 0 0 1. 0 O. 5 0. 25

Allens Media (No Added Hardness) d n 4 (l l 1 1 2 3 2 3 3- 2 3 3 2 3 3 4 0 O 0 0 1 2 0 4 4 1 2 4 1 4 4 6 0 0 0 0 0 2 O 4 4 0 1 5 0 5 5 10 0 0 0 0 1 5 0 7 7 0 4 0 9 9 1() 1 0 0 1 6 9 4 9 9 0 9 10 4 10 l() b -l- -l- -l- -l- -I- -l- -l- -l- -l- -l- 4 0 0 0 0 1 1 2 2 2 0 1 1 1 1 1 2 O 0 0 0 9 0 1 1 l 0 0 1 1 1 1 3 0 0 0 0 0 0 0 1 1 0 0 0 t) 2 2 4 0 0 0 0 0 U 0 l 1 0 0 1 U 3 4 8 0 0 0 0 0 0 9 1 1 0 0 1 1 4 4 subculture" -l- -l- -l- -I- -I- -l- Rated on scale using 0 as nil algae to 10 as maximum growth, initial algae concentration oi 7.5 millions cells/nil. equivalent to value ol 3. b denotes growth and denotes no growth.

Table 2.-Percenl reduction of sewage orgalzzsms usmg N .C. and potassium dzchloro lrzazl/zelrlo/ze 11,600/1111.lx Distilled Water, 20,500/rnl.a Distilled Water, Chlorine Minutes .Iinutes N .C. (ppm.) (ap-m) 2. 25 0 96. 9 98.0 99.8 99.9 97.1 98.1 99.2 99. 1 1. 125 0 88.8 98. 5 99.1 99.8 90.0 97. 8 99. 0 99. 4 0 1. 0 99. 1 99.9 99.9 99.9 99. 7 99.8 99.9 99.9 0 0. 5 97.9 99.4 99. 9 99.9 98. 4 99.8 99.8 99.9 0 0. 25 88. 3 97. 5 99.2 99. 9 91. 9 98. 0 99.7 99.9 O 0. 125 61.2 93. 8 9S. 5 99.7 82. 0 98. 2 99. 8 99.9 2. 25 1. 0 99. 6 99. 9 98. 9 99.9 99. 7 99.9 99.9 99.9 2. 25 0.25 S8. 5 98. 5 99. 7 99.9 99. 8 99. 0 99.8 99. 9 1. 125 0. 5 94. 0 99. 9 99.9 99. 9 97. 9 99. 9 99.9 99.9 1. 125 0. 125 78. 8 96. G 98. S 99.7 76. 1 9G. 8 99.7 99. 8

e Standard Plate Counts.

When 4 oz. of the foregoing compound Were introduced into 10,000 gallons of Water, each of the three components of the nitrogenous composition (NC.) constituted .56 p.p.m., and the released chlorine constituted .25 p.p.m. If four times the above formulation (16 oz. per 10,000 gallons of Water) were employed in 10,000 gallons of Water, the three components of the nitrogenous composition v/ould constitute 2.25 p.p.m., and the chlorine would constitute 1 p.p.m. The latter dosage would be desirable for treating a swimming pool substantially green with algae, While the first dosage would be useful for maintaining the pool in clear condition.

EXAMPLE lll The process is as described in Example Il except that the formulation is as follows:

Percent Dodecylamine hydrochloride 6.34 Trimethyl alkyl ammonium chloride 6.34

4.5 p.p.m., 2.25 p.p.m. and 1.25 p.p.m., the chlorinereleasing agent Was used alone to provide chlorine concentrations of 1.0 p.p.m., 0.5 p.p.m. and 0.25 p.p.m., and compositions of this invention containing various combinations of N.C. with a chlorine-releasing agent (sodium hypochlorite) were used. The results reported in Table lll show, for example, that treatment with a composition containing 2.25 p.p.m. of the N.C. composition and 0.5 p.p.m. released-chlorine obtains results which are quite superior to both 2.25 p.p.m. and 4.5 p.p.m. of the N.C. composition alone as well as to both 1.0 p.p.m. and 0.5 p.p.m. released-chlorine alone. Similarly, a more effective kill is obtained With a composition containing 4.5 p.p.m. of the N.C. composition and 1.0 p.p.m. releasedchlorine than are obtained When either 4.5 p.p.m. of the NC. composition of 1.0 p.p.m. released-chlorine are employed alone.

These tests were conducted in both distilled and hard Water and the standard plate count method was utilized.

T able 3.-Percent reduction of sewage organisms by N .C. and chlorine at varying contact times 21,320/ml.u Distilled Water, 31,320/rn1.n Hard Water,b N.C. Chlorine Minutes Minutes (p.p.m.) (p.p.m.)

8,260/1111. Distilled Water 8,200/ml. Hard Water u Standard plate count. b 200 p.p.m. added hardness.

Percent Methyl alkyl dipolyoxypropylene ammonium methyl sulfate 6.34 Sodium dichloro(s) triazinetrione 27.73 Sodium biphosphate 51.20 Silica 0.05

The foregoing dry formulation when added to Water is effective in destroying Chlorella pyreitodosa, Scenedesmus oblz'quus, Plzormz'dz'um inundatzm, Oscllatorz'a tennis, and a culture of settled sewage. The results are substantially as shown in Tables 1 and 2.

EXAMPLE IV the N.C. composition was used alone at concentrations of While in the vforegoing speci'cation we have set forth specific ingredients and procedure in considerable detail for the purpose of illustrating embodiments of the invention, it will be understood that such details may be varied widely by those skilled in the art without departing from the spirit ot our invention.

We claim:

Il. A germicidal composition comprising a chlorinereleasing material and a nitrogenous composition consisting of substantially equal parts of (a) dodecylamine hydrochloride, (b) trimethyl alkyl ammonium chloride, and (c) methyl alkyl dipolyoxypropylene ammonium methyl sulfate; said chlorine-releasing material being selected from the group consisting of alkaline metal di'- chloro triazinetrione, alkaline metal trichloro triazinetrione, chlorine, the reaction product of dichloro triazinetz'ione and an alkaline agent, the reaction prod-uct of trichloro triazinetrione and an alkaline agent, and alkaline metal hypochlorite, the ratio of said nitrogenous composition to released-chlorine being from 18:1 to about 1:1.

2. The composition of claim 1 containing, when in- 'roduced into water, at least 0.1 p.p.m. chlorine.

3. The composition of claim 1 in which the ingredients (a), (b) and (c) are about equal by weight and when added to Water constitute .1 to about 5 parts per million and at which the chlorine constitutes at least .1 part per million.

4. The composition of claim 1 in which the nitrogenous composition constitutes 1.125 to 2.25 p.p.m., and the released chlorine constitutes 0.1 to 1 p pm.

5. The composition of claim 1 in which each of the three components of the released nitrogenous composition constitutes about .75 p.p.m., and the chlorine constitutes .25 to 1 p.p.m.

6. The composition of claim 1 in which each of the three components of the released nitrogenous composition constitutes about .375 p.p.m., and the chlorine constitutes .125 to .5 p.p.m.

7. A germicidal composition according to claim 1 Comprising substantially equal parts by weight of:

(a) dodecylamine hydrochloride,

(b) trimethyl alkyl ammonium chloride,

(c) methyl alkyl dipolyoxypropylene ammonium methyl sulfate, and an amount of (d) potassium dichloro triazinetrione sufficient to proammonium 5. A dry germicidal composition comprising: (a) dodecylamine hydrochloride, (b) trimethyl alkyl ammonium chloride, (c) methyl alkyl dipolyoxypropylene ammonium methyl sulfate, and (d) a chlorine-releasing chemical selected from the group consisting of alkaline metal dichloro triazinetrione, alkaline metal trichloro triazinetrione, chlorine, the reaction product of trichloro triazinetrione and an alkaline agent, and alkaline metal hypochlorite, said components (a), (b), and (c) being presont in substantially equal parts and (a)-{ (b)-{(c) dening a ratio, in Water, with the chlorine released by component (d) of from 18:1 to about 1:1 and said chlorine comprising at least 0.1 p.p.m.

References Cited by the Examiner UNlTED STATES PATENTS 2,320,279 5/43 Kalusdian 252-102 2,320,280 5/43 Kalusdian 252-102 2,560,280 7/51 De Bonneville 167-22 2,607,738 S/52 Hardy 252 102 2,692,231 10/54 Stayner et al. 210-62 2,944,967 7/60 Dunklin et al. 210-64 2,987,435 6/61 Davies et al 167*22 OTHER REFERENCES Trademark Reg. No. 719,497, Arma2ide, Armour Co., Aug. 8, 1961 (date of rst public use Aug. 19, 1960).

IULTAN S. LEVTT, Prz'lfzary Examiner.

MORRS O. WGLK, lRVlNG MARCUS, LEWIS GOTTS, Examiners. 

1. A GERMICIDAL COMPOSITION COMPRISING A CHLORINERELEASING MATERIAL AND A NITROGENOUS COMPOSITION CONSISTING OF SUBSTANTIALLY EQUAL PARTS OF A (A) DODECYLAMINE HYDROCHLORIDE, (B) TRIMETHYL ALKYL AMMONIUM CHLORIDE, AND (C) METHYL ALKYL DIPOLYOXYPROPYLENE AMMONIUM METHYL SULFATE; SAID CHLORINE-RELEASING MATERIAL BEING SELECTED FROM THE GROUP CONSISTING OF ALKALINE METAL DICHLORO TRIAZINETRIONE, ALKALINE METAL TRICHLORO TRIAZINETRIONE, CHLORINE, THE REACTION PRODUCT OF DICHLORO TRIAZINETRIONE AND AN ALKALINE AGENT, THE REACTION PRODUCT OF TRICHLORO TRIAZINETRIONE AND AN ALKALINE AGENT, AND ALKALINE METAL HYPOCHLORITE, THE RATIO OF SAID NITROGENOUS COMPOSITION TO RELEASED-CHLORINE BEING FROM 18:1 TO ABOUT 1:1. 